Gravitational modulation of filler distribution in asymmetric mixed matrix membrane: Achieving high loading in skin layer

The fillers in asymmetric mixed matrix membranes (AMMMs) by phase inversion tend to distribute across the membrane, but less in the skin layer, resulting in limited enhancement of gas separation performance. In this work, an external gravity field is proposed to induce polystyrene-acrylate (PSA) modified hollow ZIF-8 nanospheres (PHZ) to settle and accumulate in the skin layer by the density difference between ZIF-8 and the polymer solution , then through phase inversion, the gravity induced AMMMs (GAMMMs) with improved ZIF-8 loading in skin layer is constructed. This is confirmed by the EDS analysis of the membrane cross-sections that more PHZ settle and accumulate in the skin layer, which enhances the filler loading by 330 % in comparison to the AMMMs without gravity sedimentation. Together with the hollow cavity of PHZ, the gas permeation can be improved greatly. Meanwhile, the PHZ can also guarantee the favorable interfacial compatibility by the hydrogen bonding interaction between the carboxyl groups in PSA with the PES polymer matrix , which is demonstrated by the slightly elevated Tg of GAMMMs over the ZIF-8/PES membrane. Consequently, the PHZ/PES GAMMMs can achieve high gas permeation while keeping sufficient selectivity at high filler loading in the skin layer. The PHZ-8d/PES GAMMM shows H 2 permeance of 29.11 GPU and H 2 /CH 4 of 83.04, which are 142.85 % and 5.99 % higher than those of ZIF-8/PES AMMM without gravity sedimentation, and exceeding the corresponding 2008 Robeson upper bound. This proposed GAMMM shows a great potential in the large-scale MMMs based gas separation.